The present invention relates to the field of single site catalyst systems based on pyridine-iminophenol, pyridine-iminoalcohol or pyridine-iminoamine complexes and suitable for oligomerising or polymerising ethylene and alpha-olefins.

A multitude of catalyst systems available for polymerising or oligomerising ethylene and alpha-olefins exist, but there is a growing need for finding new systems capable of tailoring polymers with very specific properties. More and more post-metallocene catalyst components based on early or late transition metals from Groups 3 to 10 of the Periodic Table have recently been investigated such as for example those disclosed in Gibson and al. review (Gibson, V.C.; Spitzmesser, S.K., in Chem. Rev. 2003, 103, p. 283).

Pyridine-iminophenol derivatives are known and have been described for example by Ismet et al. (Ismet, K.; Fatma, M.; Dig Dem E. in Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 42, 2717-2724, 2004) or by Asada et al. (Asada, H.; Hayashi, K.; Negoro, S.; Fujiwara, M.; Matsushita, T. in Inorganic Chemistry Communications 6, 193-196, 2003) or by Bacchi et al. (Bacchi, A.; Carcelli, M.; Pelizzi,C.; Pelizzi, G.; Pelagatti, P.; Ugolotti, S. in Eur. J. lnorg. Chem. 2179-2187, 2002), but corresponding complexes have never been described as catalysts for the polymerisation of olefins.

Matsui and Fujita (Matsui S. and Fujita T. in Catalysis Today, 2001, 66, 63-73) disclose the synthesis of ligand-oriented group 4-based catalyst components having two phenoxy-imine ligands. These were also tested in the polymerisation of ethylene at atmospheric pressure with methylaluminoxane as cocatalyst. Some exhibited fair to high activity and some displayed practically no activity.

There is still a need to improve either the specificities or the performances of these systems.

It is an aim of this invention to provide new single site catalysts based on tridentate pyridine-iminophenol, pyridine-iminoalcohol or pyridine-iminoamine.

It is another aim of the present invention to provide active catalyst systems based on these catalyst components.

It is a further aim of the present invention to provide a process for polymerising or for oligomerising ethylene and alpha-olefins with these new catalyst systems.

Any one or more of these aims is fulfilled, at least partially, by the present invention.

Accordingly, the present invention discloses metallic complexes of formula I wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, and R₉ are each independently selected from hydrogen, unsubstituted or substituted hydrocarbyl having from 1 to 20 carbon atoms, or inert functional group and two or more of those groups can themselves be linked together to form further ring or rings, with the restriction that at least one of R₁, R₇ and R₈ is not hydrogen;
wherein M is a metal Group 3 to 10 of the Periodic Table;
wherein Y is ○ or NR*, with R* being alkyl or aryl group having from 1 to 12 carbon atoms;
wherein each X can be the same or different and is selected from halogen, substituted or unsubstituted hydrocarbyl having from 1 to 20 carbon atoms, substituted or unsubstituted aryloxy or alkoxy;
wherein m is zero or an integer from 1 to 3; and
wherein (n+1) is the valence of M.

The metallic complex results from the complexation of a ligand of general formula II with metallic salt MX_n+1 in a solvent wherein R₁ to R₉ are as described hereabove.

Ligand of formula II is the reaction product of carbonylated pyridine of formula III with compound of formula IV, wherein R₁ to R₉ are as described hereabove.

The reaction conditions are well known in the art.

By inert functional group, is meant a group, other than hydrocarbyl or substituted hydrocarbyl, that is inert under the complexation conditions to which the compound containing said group is subjected. They can be selected for example from halo, ester, ether, amino, imino, nitro, cyano, carboxyl, phosphate, phosphonite, phosphine, phosphinite, thioether and amide. Preferably, they are selected from halo, such as chloro, bromo, fluoro and iodo, or ether of formula - OR* wherin R* is unsubstituted or substituted hydrocarbyl. After metallation of the ligand, an inert functional group must not coordinate to the metal more strongly than the groups organised to coordinate to the metal and thereby displace the desired coordinating group.

In preferred embodiments according to the present invention, m is zero and R₂, R₃, R₄, R₅, R₆, and R₉ are hydrogen and R₁, R₇ and R₈, can each be independently selected from hydrogen, substituted or unsubstituted hydrocarbyl having from 1 to 20 carbon atoms, halogen, nitro or cyano groups, with the restriction that at least one of them is not hydrogen.

In this description, substituted hydrocarbyls are defined as chains or links that may comprise one or more heteroatoms.

Some precursors for R₁ can advantageously be selected from aromatic or heteroaromatic boronic acids of formula wherein each R' is independently selected from hydrogen or hydrocarbyl or inert functional group.

Other precursors for R₁ can be selected from any one of the following:

Preferably, R₁, R₇, and R₈ are each independently selected from hydrogen or substituted or unsubstituted alkyl or aryl groups or halogen with the restriction that at least one of them is not hydrogen.

The preferred alkyl groups are methyl and tert-butyl.
The preferred aryl groups are unsubstituted or substituted phenyl groups.
The preferred halogen is chlorine.

Preferably all three R₁, R₇ and R₈ are not hydrogen simultaneously.

More preferably either R₇ or R₈ is present, the other being hydrogen and R₁ is one of the preferred substituent groups or hydrogen.

Preferably M is Ti, Zr, Hf, V, Cr, Mn, Fe, Co, Ni, Pd or rare earths. More preferably, it is Ti, Cr, Fe or Zr.

Preferably X is halogen, more preferably it is chlorine.

The solvent may be selected from dichloromethane or tetrahydrofuran and the complexation reaction is carried out at room temperature or at reflux.

The present invention further discloses an active catalyst system comprising the single site catalyst component of formula I and an activating agent having an ionising action.

Suitable activating agents are well known in the art. The activating agent can be an aluminium alkyl represented by formula AlR⁺_nX_3-n wherein R⁺ is an alkyl having from 1 to 20 carbon atoms and X is a halogen. The preferred alkylating agents are triisobutyl aluminium (TIBAL) or triethyl aluminium (TEAL).

Alternatively, it can be aluminoxane and comprise oligomeric linear and/or cyclic alkyl aluminoxanes represented by formula for oligomeric, linear aluminoxanes and by formula for oligomeric, cyclic aluminoxane,
wherein n is 1-40, preferably 10-20, m is 3-40, preferably 3-20 and R* is a C₁-C₈ alkyl group and preferably methyl.

Preferably, the activating agent is methylaluminoxane (MAO) or tetra-isobutyldialuminoxane (IBAO), more preferably, it is IBAO.

The amount of activating agent is selected to give an Al/M ratio of from 100 to 3000, preferably of from 500 to 2000. The amount of activating agent depends upon its nature: for IBAO the preferred Al/M ratio is of about 500, and for MAO, it is about 2000.

Suitable boron-containing activating agents may comprise a triphenylcarbenium boronate such as tetrakis-pentafluorophenyl-borato-triphenylcarbenium as described in EP-A-0427696, or those of the general formula [L'-H] + [B Ar₁ Ar₂ X₃ X₄]- as described in EP-A-0277004 (page 6, line 30 to page 7, line 7). The amount of boron -containing activating agent is selected to give B/M ratio of from 0.5 to 5, preferably of about 1.

In another embodiment, according to the present invention, the single site catalyst component of formula I may be deposited on a conventional support. Preferably, the conventional support is silica impregnated with MAO. Alternatively and preferably, it can be an activating support such as fluorinated alumina silica.

The present invention further discloses a method for preparing an active catalyst system that comprises the steps of:

1. a) providing a ligand of formula II;
2. b) complexing the ligand of step a) with a metallic salt Man+1 in a solvent;
3. c) retrieving catalyst component I;
4. d) activating with an activating agent having an ionising action;
5. e) optionally adding a cocatalyst;
6. f) retrieving an active oligomerisation or polymerisation catalyst system.

Alternatively, in step d) catalyst component I is deposited on a support impregnated with an activating agent or on an activating support containing fluor.

The cocatalyst may be selected from triethylaluminium, triisobutylaluminum, tris-n-octylaluminium, tetraisobutyldialuminoxane or diethyl zinc.

The active catalyst system is used in the oligomerisation and in the polymerisation of ethylene and alpha-olefins.

The present invention discloses a method for the oligomerisation or the homo-or co-polymerisation of ethylene and alpha-olefins that comprises the steps of:

1. a) injecting the active catalyst system into the reactor; and
2. b) injecting the monomer and optional comonomer either before or after or simultaneously with step a);
3. c) maintaining under polymerisation conditions;
4. d) retrieving the oligomers and/or polymer.

The pressure in the reactor can vary from 0.5 to 50 bars, preferably from 5 to 25 bars.

The polymerisation temperature can range from 10 to 100°C, preferably from 50 to 85°C.

Preferably the monomer and optional comonomer are selected from ethylene, propylene or 1-hexene.

In another preferred embodiment according to the present invention, the optional comonomer is a polar functionalised alpha-olefin.

• Figure 1 represents the Gel Permeation Chromatography (GPC) curve of the polyethylene resin obtained with catalyst D7 activated with IBAO, with iC4 as solvent, at a temperature of 85 °C, under an ethylene pressure of 29 bars and after a polymerisation time of 30 minutes.
• Figure, 2 represents the GPC curve of the polyethylene resin obtained with catalyst D1 activated with IBAO, with iC4 as solvent, at a temperature of 85 °C, under an ethylene pressure of 24 bars and after a polymerisation time of 30 minutes.
• Figure 3 represents the GPC curve of the polyethylene resin obtained with catalyst D7 activated with TiBAI, with iC4 as solvent and hexene as comonomer at a temperature of 85 °C, under an ethylene pressure of 24 bars and after a polymerisation time of 60 minutes.
• Figure 4 represents the GPC curve of the polyethylene resin obtained with catalyst D1 activated with IBAO, with heptane as solvent, at a temperature of 85 °C, under an ethylene pressure of 22 bars and after a polymerisation time of 30 minutes.

All reactions were performed using standard Schlenk techniques or in an argon-filled glove-box. The starting materials and reagents, purchased from commercial suppliers, were used without purification. All the solvents were dried and distilled before use either over sodium and benzophenone for toluene, pentane and THF, or over CaH₂ for ethanol. ¹H, ¹³ C and ³¹P NMR spectra were recorded on a Bruker Advance300 apparatus.

192 mg (1 mmol) of 6-bromo-2-pyridinecarboxaldehyde and 152 mg (1.2 mmol) of phenylboronic acid were dissolved in 10 mL of tetrahydrofuran (THF). 1 ml (1mmol) of Na₂CO₃ in aqueous solution (1M) and 8 mg (0.7%) of Pd(PPh₃)₄ were added. The reaction mixture was heated during 45 min, at a temperature of 130°C in a micro-wave reactor. The solution was filtered on paper, 10 ml of AcOEt were added and the organic phase was successively washed with NaHCO₃, with H₂O and with an aqueous solution of NaCl. The organic phase was dried over MgSO₄, filtered and evaporated to dryness. After a chromatography on silica gel (Pentane/Et₂O, 1/1), 136 mg of aldehyde A were obtained as colourless oil with a yield of 74%. ¹H NMR (300 MHz, CDCl₃) δ (ppm): 10.17 (s, 1 H), 8.11 (d, J=6Hz, 2H), 7.89 (m, 3H), 7.49 (m, 3H)
¹³C{¹H} NMR (75 MHz, CDCl₃)□ δ (ppm): 114.5, 119.2, 121.8, 123.7, 124.4, 132.5, 132.8, 147.5, 188.7.

Precursor (B) was prepared following the same procedure as that used to prepare precursor (A) except that 238 mg (1.2 mmol) of (2-phenyl)phenylboronic acid were used as reagent. 255 mg of precursor (B) were obtained as colourless oil with a yield of 98%. ¹H NMR (300 MHz, CDCl₃) δ (ppm): 10.09 (s, 1H), 7.79 (d, J=6Hz, 2H), 7.52 (m, 4H), 7.25 (m, 3H), 7.15 (m, 3H)
¹³C{¹H} NMR (75 MHz, CDCl₃)□ δ (ppm): 119.2, 127.0, 127.9, 128.2, 129.1, 129.5, 129.7, 130.7, 135.0, 136.1, 138.2, 140.9, 152.5, 159.9, 193.7.

Precursor (C) was prepared following the same procedure as that used to prepare precursor (A) except that 180 mg (1.2 mmol) of 2,6-(dimethyl)phenylboronic acid were used as reagent. 200 mg of precursor (C) were obtained as colourless oil with a yield of 95%. ¹H NMR (300 MHz, CDCl₃) δ (ppm): 10.13 (s, 1H), 7.96 (d, J=6Hz, 2H), 7.48 (m, 1H), 7.25 (m, 1H), 6.99 (d, J=6Hz, 2H), 2.06 (s, 6H)
¹³C{¹H} NMR (75 MHz, CDCl₃)□ δ (ppm): 15.0, 114.3, 121.5, 122.6, 123.2, 123.7, 132.1, 147.6, 188.6.

Precursor (D) was prepared following the same procedure as that used to prepare precursor (A) except that 206 mg (1.2 mmol) of 2-naphthylboronic acid were used as reagent. 190 mg of precursor (D) were obtained as colourless oil with a yield of 82%. ¹H NMR (300 MHz, COCl₃) δ (ppm): 10.21 (s, 1H), 8.01 (m, 5H), 7.80 (d, J=6Hz, 1 H), 7.55 (m, 4H)
¹³C{¹H} NMR (75 MHz, CDCl₃)□ δ (ppm): 114.6, 120.0, 120.1, 120.9, 121.6, 122.5,123.3,124.0,124.3,128.7,132.0,132.3, 148.0, 154.7, 188.6.

Precursor (E) was prepared following the same procedure as that used to prepare precursor (A) except that 376 mg (2.4 mmol) of 2-methylphenylboronic acid were used as reagent. 425 mg of precursor (E) were obtained as colourless oil with a yield of 98%. ¹H NMR (300 MHz, CDCl₃) δ (ppm): 3.90 (s, 3H), 7.06 (d, J=2.1 Hz, 1H). 7.15 (t, J=2.0Hz, 1H), 7.45 (dt, J= 2Hz and J=0.4Hz, 1H), 7.91 (m, 3H), 8.11 (dd, J=1.6Hz and J=0.7Hz, 1 H), 10.2 (s, 1H).

Precursor (F) was prepared following the same procedure as that used to prepare precursor (A) except that 216 mg (1.2 mmol) of 8-quinolineboronic acid were used as reagent. 232 mg of precursor (F) were obtained as pale yellow solid with a yield of 99%. ¹H NMR (300 MHz, CDCl₃) δ (ppm): 7.49 (dd, J=2.0Hz and J=1.0Hz, 1H), 7.74 (t, J=2.0Hz, 1H), 7.96 (d, J=2.0Hz, 1H), 8.01 (m, 2H), 8.27 (d, J=2.0Hz, 2H), 8.41 (m, 1 H), 8.98 (dd, J=1.0Hz and J=0.4Hz, 1 H), 10.22 (s, 1H).

Precursor (G) was prepared following the same procedure as that used to prepare precursor (A) except that 470 mg (2.4 mmol) of 2-trifluoromethylphenylboronic acid were used as reagent. 477 mg of precursor (G) were obtained as orange oil with a yield of 95%. ¹H NMR (300 MHz, CDCl₃) δ (ppm): 7.57 (dt, J=2.0Hz and J=0.4Hz, 2H), 7.67 (dd, J=1.6Hz and J=0.4Hz, 2H), 7.83 (d, J=1.8Hz, 1H), 7.99 (m, 2H), 10.12 (s, 1 H).

Precursor (H) was prepared following the same procedure as that used to prepare precursor (A) except that 524 mg (2.4 mmol) of dibenzofuran-4-boronic acid were used as reagent. 540 mg of precursor (H) were obtained as pale yellow solid with a yield of 99%. ¹H NMR (300 MHz, CDCl₃) δ (ppm): 7.42 (t, J=2.0Hz, 1H), 7.54 (q, J=1.9Hz, 2H), 7.67 (d, J=1.9Hz, 1H), 8.00 (t, J=2.0Hz, 2H), 8.06 (m, 2H), 8.49 (d, J=2.0Hz, 1H), 8.73 (d, J=2.0Hz, 1H), 10.24 (s, 1H).

200 µl (2 mmol) of 2-pyridinecarboxaldehyde (reagent 1) and 220 mg (2 mmol) of 2-aminophenol (reagent 2) were dissolved in 10 mL of dry ethanol. One drop of glacial acetic acid was added and the reaction mixture was stirred during 12 h. The solution was filtered on paper and the filtrate was evaporated to dryness. After a chromatography on silica gel (CH₂Cl₂, 100 ml then AcOEt 200 ml), 394 mg of ligand L1 were obtained as orange solid with a yield of 100%. ¹H NMR (300 MHz, CDCl₃) δ (ppm): 8.83 (s, 1 H), 8.72 (d, J=6Hz, 1H), 8.17 (d, J=9Hz, 1H), 7.83 (t, J=6Hz, 1H), 7.38 (m, 2H), 7.22 (d, J=9_Hz, 1H), 7.03 (d, J=9Hz, 1 H), 6.95 (t, J=9Hz, 1 H)
¹³C{¹H} NMR (75 MHz, CDCl₃)□ δ (ppm): 115.4, 116.1, 120.2, 121.8, 125.2, 129.9, 134.5, 136.8, 149.7, 152.8, 154.1, 156.7.

Ligand L2 was prepared following the same procedure as that used to prepare ligand L1 except that 200 µl (2 mmol) of 2-phenylglycinol were used as reagent 2. 196 mg of ligand L2 were obtained yellow oil with a yield of 43 %.

¹H NMR (300 MHz, CD₂Cl₂) δ (ppm): 8.58 (m, 1H), 8.44 (s, 1 H), 8.00 (d, J=9Hz, 1H), 7.70 (t, J=9Hz, 1H), 7.40-7.26 (m, 6H), 4.53 (m, 1H), 3.90-3.63 (m, 2H), 2.90 (bs, 1 H).

Ligand L3 was prepared following the same procedure as that used to prepare ligand L1 except that 635 mg (5 mmol) of 2-amino-4-methyl-phenol were used as reagent 2. 850 mg of ligand L3 were obtained as yellow-green solid with a yield of 80 %. ¹H NMR (300 MHz, CDCl₃) δ (ppm): 8.82 (s, 1H), 8.73 (d, J=6Hz, 1H), 8.19 (d, J=9Hz, 1H), 7.83 (t, J=6Hz, 1H), 7.40 (m, 1H), 7.20 (s, 1 H), 7.05 (d, J=9Hz, 1 H), 6.92 (d, J=9Hz, 1 H), 2.31 (s, 3H)
¹³C(¹H) NMR (75 MHz, CD₂Cl₂) δ (ppm): 21.0, 115.5, 117.4, 122.0, 125.7, 130.1, 130.9, 134.9, 137.1, 150.3, 151.1, 155.0, 157.8.

Ligand L4 was prepared following the same procedure as that used to prepare ligand L1 except that 628 mg (5 mmol) of 2-amino-5-methyl-phénol were used as reagent 2. 928 mg of ligand L4 were obtained as light brown solid with a yield of 87 %.

¹H NMR (300 MHz, CDCl₃) δ (ppm): 8.81 (s, 1H), 8.71 (d, J=6Hz, 1H), 8.18 (d, J=9Hz, 1H), 7.81 (t, J=6Hz, 1H), 7.37 (m, 1H), 7.31 (d, J=9Hz, 1H), 6.86 (s, 1H), 6.73 (d, J=9Hz, 1 H), 2.35 (s, 3H)
¹³C{¹H} NMR (75 MHz, CD₂Cl₂)□ δ (ppm): 21.8, 116.2, 116.4, 121.6, 122.0, 125.6, 132.7, 137.2, 141.2, 150.3, 153.3, 155.1, 156.6.

Ligand L5 was prepared following the same procedure as that used to prepare ligand L1 except that 852 mg (5 mmol) of 2-amino-4-tertbutyl-phénol were used as reagent 2. 1353 mg of ligand L5 were obtained as yellow-green solid with a yield of 99 %.

¹H NMR (300 MHz, CDCl₃) δ (ppm): 8.88 (s, 1H), 8.72 (d, J=6Hz, 1H), 8.21 (d, J=9Hz, 1H), 7.83 (t, J=6Hz, 1H), 7.43 (d, J=6Hz, 1H), 7.39 (m, 1H), 7.30 (d, J=9Hz, 1 H), 7.12 (bs, 1H), 6.97 (d, J=9Hz, 1 H), 1.33 (s, 9H)
¹³C{¹H} NMR (75 MHz, CD₂Cl₂)□ δ (ppm): 31.8, 34.8, 113.7, 115.1, 121.9, 125.7, 127.5, 129.3, 134.5, 137.1, 143.8, 150.3, 150.9, 157.8.

Ligand L6 was prepared following the same procedure as that used to prepare ligand L1 except that 1029 mg (5 mmol) of 2-amino-3-methyl-phénol were used as reagent 2. 1355 mg of ligand L6 were obtained as brown-red solid with a yield of 99 %.

¹H NMR (300 MHz, CDCl₃) δ (ppm): 8.94 (s, 1 H), 8.81 (d, J=6Hz, 1H), 8.10 (d, J=9Hz, 1 H), 7.87 (t, J=6Hz, 1 H), 7.63-7.31 (m, 8H), 7.12 (d, J=9Hz, 1 H)
¹³C{¹H} NMR (75 MHz, CD₂Cl₂)□ δ (ppm): 115.5, 116.1, 122.3, 125.9, 127.2, 127.4, 129.0, 129.3, 134.0, 135.5, 137.3, 141.1, 150.4, 152.8, 154.8, 158.5.

Ligand L7 was prepared following the same procedure as that used to prepare ligand L1 except that 740 mg (5 mmol) of 2-amino-4-chloro-phénol were used as reagent 2. 1203 mg of ligand L7 were obtained as brown solid with a yield of 99 %. ¹H NMR (300 MHz, CDCl₃) δ (ppm): 8.79 (s, 1H), 8.74 (d, J=6Hz, 1H), 8.18 (d, J=9Hz, 1H), 7.83 (t, J=6Hz, 1H), 7.43 (m, 1H), 7.38 (d, J=6Hz, 1H), 7.21 (dd, J=2Hz, J=9Hz, 1 H), 6.98 (d, J=9Hz, 1 H)
¹³C{¹H} NMR (75 MHz, CDCl₃)□ δ (ppm): 116.3; 116.4; 121.8; 125.1; 125.5; 129.4; 135.1; 136.6; 149.8; 151.1; 153.7; 158.3.

Ligand L8 was prepared following the same procedure as that used to prepare ligand L1 except that 803 mg (5 mmol) of 2-amino-4-nitro-phénol were used as reagent 2. 1029 mg of ligand L8 were obtained as beige solid with a yield of 85 %. ¹H NMR (300 MHz, CD₂Cl₂) δ (ppm): 8.93 (s, 1H), 8.73 (d, J=6Hz, 1 H), 8.34 (d, J=6Hz, 1 H), 8.21 (d, J=9Hz, 1 H), 8.14 (dd, J=9Hz, 1H), 7.86 (t, J=9Hz, 1 H), 7.44 (m, 1H), 7.09 (d, J=9Hz, 1 H).

Ligand L9 was prepared following the same procedure as that used to prepare ligand L1 except that 184 mg (1 mmol) of precursor A were used as reagent 1. 261 mg of ligand L9 were obtained as yellow solid with a yield of 95 %.

Ligand L10 was prepared following the same procedure as that used to prepare ligand L1 except that 99 mg (1 mmol) of precursor C were used as reagent 1. 261 mg of ligand L10 were obtained as yellow solid with a yield of 95 %.

Ligand L11 was prepared following the same procedure as that used to prepare ligand L1 except that 233 mg (1 mmol) of precursor D were used as reagent 1. 149 mg of ligand L11 were obtained as yellow solid with a yield of 46 %. ¹H NMR (300 MHz, CD₂Cl₂) δ (ppm): 8.92 (s,1H), 8.28 (d, J=6Hz, 1H), 8.10 (d, J=6Hz, 1H), 7.96 (m, 3H), 7.68-7.41 (m, 7H), 7.23 (t, J=6Hz, 1H), 7.01 (d, J=6Hz, 1 H), 6.88 (t, J=6Hz, 1 H)
¹³C{¹H} NMR (75 MHz, CD₂Cl₂)□ δ (ppm): 115.7, 116.9, 120.2, 120.8, 125.9, 126.1, 126.5, 127.0, 127.2, 128.1, 128.9, 129.6, 130.4, 134.5, 137.7, 154.7, 158.6.

Ligand L12 was prepared following the same procedure as that used to prepare ligand L1 except that 259 mg (1 mmol) of precursor B were used as reagent 1. 266 mg of ligand L12 were obtained as yellow solid with a yield of 67 %. ¹H NMR (300 MHz, CDCl₃) δ (ppm): 8.81 (s, 1H), 8.03(d, J=6Hz, 1H), 7.71-7.31 (m,7H), 7.21-6.92 (m, 8H).

Ligand L13 was prepared following the same procedure as that used to prepare ligand L1 except that 183 mg (1 mmol) of precursor A were used as reagent 1 and 154 mg (1 mmol) of 2-amino-4-nitrophénol as reagent 2. 240 mg of ligand L13 were obtained as yellow solid with a yield of 75 %. ¹H NMR (300 MHz, CD₂Cl₂) δ (ppm): 9.02 (s,1H), 8.38 (d, J=3Hz, 1 H), 8.12 (d, J=9Hz, 2H), 8.08 (d, J=9Hz, 2H), 7.90 (m, 2H), 7.53-7.42 (m, 3H), 7.10 (d, J=9Hz, 1 H).

Ligand L14 was prepared following the same procedure as that used to prepare ligand L1 except that 211 mg (1 mmol) of precursor C were used as reagent 1 and 154 mg (1 mmol) of 2-amino-4-nitrophénol as reagent 2. 108 mg of ligand L14 were obtained as yellow solid with a yield of 31 %. ¹H NMR (300 MHz, CD₂Cl₂) δ (ppm): 8.92 (s,1H), 8.31 (d, J=3Hz, 1H), 8.12 (d, J=9Hz, 1H), 8.05-7.88 (m, 2H), 7.40 (d, J=9Hz, 1 H), 7.20 (t, J=9Hz, 1H), 7.10 (d, J=9Hz, 2H), 6.90 (d,J=9Hz, 1 H), 2.03 (s, 6H).

Ligand L15 was prepared following the same procedure as that used to prepare ligand L1 except that 233 mg (1 mmol) of precursor D were used as reagent 1 and 154 mg (1 mmol) of 2-amino-4-nitrophénol as reagent 2. 320 mg of ligand L15 were obtained as yellow solid with a yield of 86 %. ¹H NMR (300 MHz, CD₂Cl₂) δ (ppm): 9.02 (s,1H), 8.35 (d, J=3Hz, 1 H), 8.26 (d, J=9Hz, 1 H), 8.16-8.04 (m, 2H), 7.98 (t, J=9Hz, 1H), 7.96-7.92 (m, 2H), 7.72 (d, J=9Hz, 1 H), 7.63-7.48 (m, 4H), 7.09 (d, J=9Hz, 1 H), 2.03 (s, 6H).

Ligand L16 was prepared following the same procedure as that used to prepare ligand L1 except that 259 mg (1 mmol) of precursor B were used as reagent 1 and 154 mg (1 mmol) of 2-amino-4-nitrophénol as reagent 2. 390 mg of ligand L16 were obtained as yellow solid with a yield of 98 %. ¹H NMR (300 MHz, CD₂Cl₂) δ (ppm): 8.90 (s,1H), 8.32 (s, 1H), 8.14 (m, 1 H), 8.01 (d, J=9Hz, 1 H), 7.73 (m, 1 H), 7.55-7.46 (m, 5H), 7.24-7.04 (m, 6H).

Ligand L17 was prepared following the same procedure as that used to prepare ligand L1 except that 247 mg (1 mmol) of 2 picoline-6-carboxaldehyde were used as reagent 1 and 220 mg (2 mmol) of 2-aminophenol as reagent 2. 328 mg of ligand L17 were obtained as yellow solid with a yield of 77 %. ¹H NMR (300 MHz, CDCl₃) δ (ppm) : 2.63 (s, 3H), 6.75 (s, 1H), 6.95 (dt, J=2Hz and J=0.5Hz, 1H), 7.02 (dd, J=2Hz and J=0.3Hz, 1H), 7.26 (dt, J=2Hz and J=0.5Hz, 1 H), 7.30 (d, J=2Hz, 1H), 7.43 (dd, J=2Hz and 0.4Hz, 1H), 7.77 (t, J=2Hz,1 H), 8.01 (d, J=2Hz, 1 H), 8.82 (s, 1 H).

Ligand L18 was prepared following the same procedure as that used to prepare ligand L1 except that 247 mg (1 mmol) of picoline-6-carboxaldehyde were used as reagent 1 and 321 mg (2 mmol) of 2-amino-4-phenol as reagent 2. 235 mg of ligand L18 were obtained as beige solid with a yield of 46 %. ¹H NMR (300 MHz, DMSO) δ (ppm) : 2.55 (s, 3H), 7.09 (d, J=2.4Hz, 1H), 7.41 (d, J=1.9Hz, 1 H), 7.86 (t, J=2Hz, 1 H), 8.05 (m, 3H), 8.68 (s, 1 H), 11.0 (s, 1 H).

Ligand L19 was prepared following the same procedure as that used to prepare ligand L1 except that 640 mg (1 mmol) of precursor E were used as reagent 1 and 482 mg (3 mmol) of 2-amino-4-nitrophenol as reagent 2. 747 mg of ligand L18 were obtained as orange brown solid with a yield of 71 %. ¹H NMR (300 MHz, CD₂Cl₂) δ (ppm): 3.91 (s,3H), 7.10 (q, J=2.3Hz, 3H), 7.44 (m, 2H), 7.86 (dd, J=0.4Hz and J=2.0Hz, 1H), 7.93 (d, J=1.9Hz, 1 H), 8.02 (d, J=1.9Hz, 1H), 8.12 (d, J=1.9Hz, 1H), 8.25 (dd, J=0.6Hz and J=2.0Hz, 1H), 8.40 (d, J=0.6Hz, 1 H), 9.03 (s, 1 H).

Ligand L20 was prepared following the same procedure as that used to prepare ligand L1 except that 767 mg (4 mmol) of 6-bromo-2-pyridine carboxaldehyde were used as reagent 1 and 642 mg (4 mmol) of 2-amino-4-phenol as reagent 2. 1.20 g of ligand L20 were obtained as beige solid with a yield of 92 %. ¹H NMR (300 MHz, DMSO) δ (ppm) : 7.12 (d, J=2.2Hz, 1H), 7.83 (d, J=2.0Hz, 1H), 7.98 (t, J=1.9Hz, 1H), 8.08 (dd, J=2.2Hz and J=0.7Hz, 1H), 8.15 (d, J=0.7Hz, 1 H), 8.36 (d, J=1.9Hz, 1 H), 8.75 (s, 1 H), 11.0 (s, 1H).
¹³C{¹H} NMR (75 MHz, DMSO)□ δ (ppm): 115.7, 116.0, 120.9, 120.8, 123.4, 129.6, 136.7, 139.4, 139.7, 140.5, 154.5, 157.0, 160.6.

Ligand L21 was prepared following the same procedure as that used to prepare ligand L1 except that 469 mg (2 mmol) of precursor F were used as reagent 1 and 220 mg (2 mmol) of 2-aminophenol as reagent 2. 389 mg of ligand L21 were obtained as beige solid with a yield of 60 %. ¹H NMR (300 MHz, DMSO) δ (ppm) : 6.95 (d, J=2.1Hz, 1 H), 7.10 (dd, J=2.0Hz and 0.5Hz, 1 H), 7.38 (d, J=0.5Hz, 1 H), 7.61 (q, J=1.0Hz, 1 H), 7.77 (t, J=2.0Hz, 1H), 8.06 (m, 2H), 8.20 (t, J=3.3Hz, 2H), 8.39 (d, J=3.3Hz, 1H), 8.45 (d, J=3.3Hz, 1 H), 8.80 (s, 1 H), 8.97 (d, J=0.7Hz, 1 H), 9.58 (s, 1H).

Ligand L22 was prepared following the same procedure as that used to prepare ligand L1 except that 469 mg (2 mmol) of precursor F were used as reagent 1 and 321 mg (2 mmol) of 2-amino-4-nitrophenol as reagent 2. 538 mg of ligand L22 were obtained as beige solid with a yield of 73 %. ¹H NMR (300 MHz, DMSO) δ (ppm) : 6.75 (d, J=2.1Hz, 1H), 7.38 (dd, J=2.2Hz and 0.7Hz, 1H), 7.45 (d, J=0.7Hz, 1H), 7.62 (dd, J=1.0Hz and J=2.1Hz, 1H), 7.79 (t, J=2.0Hz, 1H), 7.97 (d, J=2.2Hz, 1H), 8.10 (m, 2H), 8.22 (dd, J=1.8Hz and J=0.3Hz, 1H), 8.41 (dd, J=1.7 and J=0.2Hz, 1H), 8.51 (dd, J=1.6Hz and J=0.4Hz, 1 H), 8.96 (dd, J=1.0Hz and J=0.4Hz, 1 H), 10.1 (s, 1 H).

Ligand L23 was prepared following the same procedure as that used to prepare ligand L1 except that 628 mg (2.5 mmol) of precursor G were used as reagent 1 and 276 mg (2.5 mmol) of 2-aminophenol as reagent 2. 612 mg of ligand L23 were obtained as brown solid with a yield of 72 %.

Ligand L24 was prepared following the same procedure as that used to prepare ligand L1 except that 628 mg (2.5 mmol) of precursor G were used as reagent 1 and 401 mg (2.5 mmol) of 2-amino-4-nitrophenol as reagent 2. 658 mg of ligand L24 were obtained as beige solid with a yield of 68 %. ¹H NMR (300 MHz, DMSO) δ (ppm) :7.10 (d, J=2.2Hz, 1H), 7.67 (dt, J=1.9Hz and 3.4Hz, 3H), 7.79 (d, J=1.9Hz, 1H), 7.90 (d, J=2.0Hz, 1H), 8.08 (m, 3H), 8.37 (d, J=2.0Hz,1 H), 8.75 (s, 1H), 11.00 (s, 1 H).

Ligand L25 was prepared following the same procedure as that used to prepare ligand L1 except that 547 mg (2 mmol) of precursor H were used as reagent 1 and 220 mg (2 mmol) of 2-aminophenol as reagent 2. 597 mg of ligand L25 were obtained as pale orange solid with a yield of 82 %. ¹H NMR (300 MHz, CD₂Cl₂) δ (ppm) :7.00 (t, J=1.8Hz, 1H), 7.05 (d, J=2.0Hz, 1 H), 7.30 (t, J=1.8Hz, 1 H), 7.45 (t, J=1.8Hz, 2H), 7.55 (q, J=1.9Hz, 3H), 7.71 (d, J=2.0Hz, 1H), 8.04 (m, 3H), 8.26 (d, J=1.9Hz, 1H), 8.47 (d, J=1.8Hz, 1H), 8.60 (d, J=2.0Hz, 1 H), 9.00 (s, 1 H).

Ligand L26 was prepared following the same procedure as that used to prepare ligand L1 except that 547 mg (2 mmol) of precursor H were used as reagent 1 and 321 mg (2 mmol) of 2-amino-4-nitrophenol as reagent 2. 603 mg of ligand L26 were obtained as beige orange solid with a yield of 74 %. ¹H NMR (300 MHz, DMSO) δ (ppm) :6.76 (d, J=2.3Hz, 1H), 7.47 (t, J=1.9Hz, 1 H), 7.59 (dt, J=1.7Hz, 2H), 7.83 (d, J=2.0Hz, 1H), 7.98 (dd, J=1.9Hz, 1 H), 8.16 (m, 5H), 8.40 (t, J=1.7Hz, 2H), 8.58 (d, J=2.0Hz, 1H), 8.90 (s, 1H).

450 µl (3 mmol) of 2-acetylpyridine (reagent 1), 331 mg (3 mmol) of 2-aminophenol (reagent 2) and a few mg of para toluene sulfonic acid were dissolved in 20 mL of dry toluene. The reaction mixture was stirred at a temperature of 140°C for a period of time of 3 days. The solution was evaporated to dryness. After a chromatography on silica gel (heptane/AcOEt 8:2), 208 mg of ligand L27 were obtained as yellow solid with a yield of 33%. ¹H NMR (300 MHz, CD₂Cl₂) δ (ppm) :2.43 (s, 3H), 6.66 (t, J=1.9Hz, 1H), 6.83 (dd, J=2.5Hz and J=1.7Hz, 1H), 7.06 (m, 1 H), 7.22 (s, 1H), 7.45 (dt, J=2.3Hz, 1 H), 7.69 (m, 2H), 8.61 (dt, J=1.1Hz, 1H), 10.01 (dt, J=1.8Hz, 1 H).

Ligand L28 was prepared following the same procedure as that used to prepare ligand L27 except that 300µL (2 mmol) of 2-acetylpyridine were used as reagent 1 and 321 mg (2 mmol) of 2-amino-4-nitrophenol as reagent 2. 156 mg of ligand L28 were obtained as dark yellow solid with a yield of 30 %. ¹H NMR (300 MHz, CD₂Cl₂) δ (ppm) : 2.42 (s, 3H), 6.66 (t, J=1.7Hz, 1H), 6.82 (t, J=2.0Hz, 1 H), 7.05 (m, 1H), 7.21 (s, 1 H), 7.43 (dd, J=2.3Hz, 1H), 7.67 (m, 2H), 8.60 (dd, J=1.2Hz, 1 H), 10.00 (dd, J=1.9Hz, 1H).

561 µl (5 mmol) of 2-pyridinecarboxaldehyde (reagent 1) and 376 mg (5 mmol) of 3-amino-1-propanol (reagent 2) were dissolved in 10 mL of dry ethanol and the reaction mixture was stirred during 24h. The solution was evaporated to dryness and the resulting oil was washed with pentane. Ligand L29 was obtained as yellow oil with a yield of 99%. ¹H NMR (300 MHz, CDCl₃) δ (ppm) : 2.00 (q, J=1.5Hz, 2H), 2.37 (s, 3H), 3.69 (t, J=1.6Hz, 2H), 3.92 (t, J=1.3Hz, 2H), 7.28 (t, J=2.2, 1 H), 7.69 (t, J=1.9Hz, 1H), 7.93 (d, J=2.0, 1 H), 8.58 (d, J=1.0Hz, 1 H).

198 mg (1 mmol) of ligand L1 was dissolved in 5 mL of THF and cooled to a temperature of -78°C. 1 mmol of n-butyl lithium (1,6M in hexane) was added drop-wise. The orange solution was stirred for 2 hours at room temperature. 1 mL (1 mmol) of TiCl₄ (1M in toluene) was dissolved in 5 mL of THF and cooled to a temperature of -78°C. The solution of the anionic ligand was added drop-wise to the solution of TiCl₄. The resulting solution was stirred overnight at room temperature. The mixture was evaporated to dryness and the complex was extracted with 10 mL of dry dichloromethane. The filtrate was evaporated and the residue was washed with 3 mL of diethyl ether, with 10 mL of pentane, and with another 10 mL of pentane. The resulting solid was dried under vacuum to afford 266 mg of complex A1 as brown-red powder with a yield of 76%.

Complexes A3, A4, A5, A6, A7, A8, A11, A12, A13, A14, A15, A16, A17, A18, A22, A23, A24, A25, A26, A27 and A29 were obtained from ligands L3, L4, L5, L6, L7, L8, L11, L12, L13, L14, L15, L16, L17, L18, L22, L23, L24, L25, L26, L27 and L29 following the same procedure as that used for obtaining complex A1 from ligand L1.

The yields are summarised in Table I. Ligand Complex Color of complex Yield (%) L3 A3 Dark red 70 L4 A4 brown 60 L5 A5 Dark red 98 L6 A6 Dark red 99 L7 A7 Dark red 98 L8 A8 Dark yellow 76 L11 A11 Dark red 89 L12 A12 Dark red 67 L13 A13 brown 54 L14 A14 brown 61 L15 A15 Dark yellow 61 L16 A16 beige 82 L17 A17 brown 99 L18 A18 Dark red 99 L22 A22 Dark yellow 13 L23 A23 brown 84 L24 A24 brown 72 L25 A25 red 70 L26 A26 Dark red 46 L27 A27 red 21 L29 A29 yellow 46

0,8 mmol of ligand L1 was dissolved in 5 mL of THF and cooled to a temperature of -78°C. 0,8 mmol of n-butyl lithium (1.6 M in hexane) were added drop-wise. The solution was stirred for 30 minutes at room temperature. 0,8 mmol of ZrCl₄ were dissolved in 5 mL of THF and cooled to a temperature of -78°C. The solution of the anionic ligand was added drop-wise to the solution of ZrCl₄. The resulting solution was stirred overnight under reflux at a temperature of 70°C. The mixture was concentrated to approximately 2 mL then 3mL of diethyl ether and 10 mL of pentane were added. Solvents were filtered off and the solid was washed twice with pentane. The resulting solid was dried under vacuum to afford 140 mg of complex B1 as orange powder with a yield of 47 %.

Similarly, Zr(IV) complex B27 was obtained from ligand L27 as an orange powder with a yield of 77 %.

Similarly, Zr(lV) complex B29 was obtained from ligand L29 as a yellow powder with a yield of 76 %.

150 mg (0,8 mmol) of ligand L1 were dissolved in 5 mL of THF and cooled to a temperature of -78°C. 0,8 mmol of n-butyl lithium (1.6 M in hexane) were added drop-wise. The solution was stirred for 30 minutes at room temperature. 0,8 mmol of (THF)₃VCl₃ were dissolved in 5 mL of THF and cooled to a temperature of -78°C. The solution of the anionic ligand was added drop-wise to the solution of VCl₃. The resulting solution was stirred overnight at room temperature. The mixture was evaporated to dryness and the complex was extracted with 10 mL of dry dichloromethane. The filtrate was concentrated to approximately 2 mL, and 10 mL of pentane were added. Solvents were filtered off and the solid was washed twice with pentane. The resulting solid was dried under vacuum to afford 233 mg of complex C1 as brown powder with a yield of 97 %.

Similarly, V(III) complex C27 was obtained from ligand L27 as a dark orange powder with a yield of 62 %.

Similarly, V(III) complex C29 was obtained from ligand L29 as a dark red powder with a yield of 99 %.

100 mg (0.26 mmol) of ligand L1 was dissolved in 5 mL of THF and cooled to a temperature of -15°C. 1 mmol of n-butyl lithium (1,6M in hexane) was added drop-wise. The solution was stirred for 30 minutes and added to a solution of 101 mg (0.26 mmol) of (THF)₃CrCl₃ dissolved in 5 mL of THF. The resulting solution was stirred overnight at room temperature. The mixture was concentrated to approximately 2 mL and 10 mL of pentane were added. Solvents were filtered off and the solid was washed twice with pentane. The resulting solid was dried under vacuum to afford complex D1 as a red powder with a yield of 93 %.

Complexes D3, D4, D5, D6, D7, D8, D21, D22, D23, D24, D25, D26, D27 and D29 were obtained from ligands L3, L4, L5, L6, L7, L8, L21, L22, L23, L24, L25, L26, L27 and L29 following the same procedure as that used for obtaining complex D1 from ligand L1.

The yields are summarised in Table II. Ligand Complex Color of complex Yield (%) L3 D3 dark red 99 L4 D4 red 89 L5 D5 Dark red 66 L6 D6 purple 99 L7 D7 red 99 L8 D8 brown 93 L21 D21 black 99 L22 D22 red 99 L23 D23 Dark red 75 L24 D24 brown 99 L25 D25 red 99 L26 D26 brown 99 L27 D27 Dark yellow 99 L29 D29 Green 99

150 mg (0.8 mmol) of ligand L1 were dissolved in 5 mL of THF and cooled to a temperature of -15°C. 0.8 mmol of n-butyl lithium (C=1,6M in hexane) were added dropwise. The solution was stirred for 30 minutes and added to a solution of 127 mg (0.8 mmol) of anhydrous FeCl₃ dissolved in 5 mL of THF. The solution was stirred at room temperature overnight. The mixture was concentrated to approximately 2 mL and then 10 mL of pentane were added. Solvents were filtered off and the solid was washed twice with pentane. The resulting solid was dried under vacuum to afford complex E1 as black powder with a yield of 92%.

Ethylene polymerisation reactions were performed in a 20 mL stainless steel autoclave containing a glass insert, fitted with mechanical stirring, external thermocouple and pressure gauge and controlled by a computer. In a typical reaction run, the temperature was set at 50°C or 80°C and 4 mL of dry solvent (toluene or n-heptane) were introduced into the reactor under nitrogen flow. In an argon-filled glove box, about 4 mg (5 µmol) of the appropriate catalyst were weighted, activated with methylaluminoxane (MAO) activator (30 % wt in toluene) in an appropriate amount to obtain a ratio [Al]:[M] of 2000 and diluted with toluene to obtain a final volume of 2 mL. 200 µL of the solution of activated catalyst were placed inside the reactor. The injection loop was rinsed with 800 µL of solvent. The ethylene pressure was raised to 15 bars and ethylene was fed continuously into the reactor. After 1 hour or an ethylene consumption of 12 mmol, the reactor was cooled down and depressurised, then the reaction was quenched with isopropanol and the solution analysed by gas chromatography. The gas chromatographic (GC) analysis of the reaction products was performed on a Trace GC apparatus with a Petrocol capillary column (methyl silicone, 100 m long, i.d. 0.25 mm and film thickness of 0.5 µm) working at a temperature of 35°C for 15 min and then heating at a rate of 5° per minute up to a temperature of 250°C. The polymerisation results are displayed in Tables III for titanium complex and in Table IV for chromium complexes. GPC measurement could not be performed on all polymers because most polymers were not fully soluble in hot trichlorobenzene (140 to 180 °C) that was used as solvent. Run Complex solvent T(°C) mPE (mg) Activity (kg/mol/h) DSC Tm (°C) (J.g^-1) 1 A1 toluene 80 174 341 133 146,8 2 A1 n-heptane 80 644 1247 133 104,2 3 A1 toluene 50 166 324 136 148,0 4 A1 n-heptane 50 367 719 133 98,6 A29 n-heptane 80 453 910 * *

All reactions were performed with 0.5 µmol of catalyst dissolved in 5 mL of solvent and MAO was added to give a [Al]:[Ti] ratio of 2000. Activities are expressed in kg of polyethylene per mol Ti per hour.
The obtained polymers were insoluble in hot trichlorobenzene and could not be caracterised by GPC. Run Complex m PE (mg) Activity (kg/mol/h) DSC Tm (°C) ΔH (J.g^-1) 5 D1 135 271 129 195,2 6 D3 129 252 131 169,5 7 D4 54 104 130 205,3 8 D5 162 312 127 193,1 9 D6 117 227 128 209,2 10 D7 158 320 130 181,9 11 D8 139 281 131 175 12 D1 77 154 129 210,5 13 D3 119 235 130 156,9 14 D4 79 152 129 178,0 15 D5 80 152 128 217,4 16 D6 75 153 130 218,3 17 D7 76 154 131 183,2 18 D8 91 190 131 120,6

All reactions were performed with 0.5 µmol of catalyst dissolved in 5 mL of solvent, and MAO was added to give a [Al]:[Cr] ratio of 2000. Runs 5 to 11 were performed in toluene and runs 12 to 18 were performed in n-heptane. Activities are expressed in kg of polyethylene per mol Cr per hour. ¹³C NMR analysis showed no short branches.

The obtained polymers were insoluble in hot trichlorobenzene and could not be caracterised by GPC.

The procedure was the same as that described above with MAO except that the catalyst was activated with an appropriate amount of tetra-isobutyldialuminoxane ((iBu)₂-Al-O-Al-(iBu)₂) (10% wt in toluene). The polymerisation results are displayed in Table V. Run Complex m PE (mg) Activity (kg/mol/h) 19 D1 293 588 20 D3 380 728 21 D4 271 534 22 D5 309 631 23 D6 348 690 24 D7 335 701 25 D8 208 380 26 D1 299 600 27 D3 398 761 28 D4 267 526 29 D5 528 1075 30 D6 390 774 31 D7 612 1293 32 D8 269 492

All reactions were performed with 0.5 µmol of catalyst dissolved in 5 mL of toluene, at a temperature of 50°C, under an ethylene pressure of 15 bars. The amount of activating agent IBAO was adjusted to yield a ratio [Al]:[Cr] of 500. Runs 19 to 25 were performed in toluene and runs 26 to 32 were carried out in n-heptane.
Activities are expressed in kg of polyethylene per mol of Cr per hour.

When the catalyst components of the present invention are activated with IBAO, they exhibit a better activity than when activated with MAO. Without wishing to be bound by a theory, it is believed that IBAO, having a well defined structure, has a better activating efficiency than MAO that comes in oligomeric with residual trimethyaluminium.

The obtained polymers were insoluble in hot trichlorobenzene and could not be caracterised by GPC.

Ethylene polymerisation reactions were carried out in a 130 ml stainless steel autoclave equipped with mechanical stirring and a stainless steel injection cylinder. In a typical reaction run, the reactor was first dried under nitrogen flow at 100°C during 10 min. Then it was cooled down to the reaction temperature (50°C, 85°C or 95 °C) and 35 ml of isobutane were introduced into the reactor with a syringe pump, followed by the comonomer if required. The pressure was adjusted to the desired value (14.8, 23.8, 29 or 33 bar) with ethylene. In an argon-filled glove box, TiBAl (10 % wt in hexane), the appropriate supported catalyst (2 or 4 % wt based on the total weight of the supported catalyst, on MAO impregnated silica) and n-hexane were placed into the injection cylinder. The valve was closed and the cylinder was connected to the reactor under nitrogen flow. The active catalyst mixture was then introduced into the reactor with 40 ml of isobutane. After 1 hour, the reactor was cooled down to room temperature and slowly depressurised, and the polymer was recovered. The comonomer, when present was hexene. The polymerisation results are displayed in Table VI. Complex Supporte d catalyst (mg) Hexene (ml) m PE (g) Prod. (g/g.h) Tm DSC (°C) SCB ¹³C NMR Mw^f kDa Mn kDa PDI A1 (2 wt %) 123.4 / 2.4 19.4 131.9 0 Ins. A1 (2 wt %) 124.1 1.6 1.3 10.5 123.5 0.5 mol % (1.5wt%C6 ) Ins. A1 (2 wt %) 124.0 / 4.1 33.3^a 133.7 < 0.1% Ins. D7 (4 wt % 304.4 / 1.6 5.3^b / < 0.1% Ins. D7 (4 wt %) 304.8 1.6 1.2 3.9 125.9 0.5 mol % (1.5wt%C6 ) 234.7 7.78 30.2 B7 4wt% 300.9 / 2.2 14.6^c 128.9 / 538.6 10.69 50.4 B1 4wt% 302.2 / 3.0 19.9^d / / / B1 4wt% 300.8 / 2.2 7.3^e 129.2 <0.1 mol% 228.8 12.97 17.6 C1 2wt% 300.8 / 1.2 3.9 / / / C1 2wt% 301.1 / 1.3 4.3 / / / All reactions were performed in isobutane, at a polymerisation temperature of 85°C, under an ethylene pressure of 23.8 bars, with 25.6 mg of TiBAl as cocatalyst. Polymerisations were stopped after a period of time of 1 hour.
^a at 29 bar with 44.7 mg of tris-n-octyl-aluminium (TnOAI) instead of TIBAI.
^b at 50°C under 14.8 bars of ethylene.
^c at 29 bar with 156 mg of IBAO instead of TiBAI ; 30 min. instead of 1 h.
^d at 95°C and 33 bar with 130 mg of IBAO instead of TiBAl ; 30 min. instead of 1 h.
^e 130 mg of IBAO instead of TiBAl.
^f Calculated for the curve between log(M) 3 to 8. For GPC curves, see figures 1 to 3.
Ins. means insoluble.

The procedure was the same as that described above with MAO in paragraph IV.a except that the reactor was first pressurised with hydrogen, followed by ethylene to reach a final pressure of 19 bar. The polymerisation results are displayed in Table VII. Run Complex [H₂]:[Ti] m Polymer (mg) Activity (kg/mol/h) DSC GPC Tm (°C) ΔH (J.g^-1) Mw Mn PDI 33 A1 0.06 78 152 129 160.4 278100 9430 29.5 34 A1 0.11 61 119 128 179.8 201800 7160 28.2 35 A1 0.17 69 135 128 173.7 insoluble 36 A1 0.20 60 117 128 160.3 218000 8400 26.0

The reaction was performed with 0.5 µmol of catalyst dissolved in 5 mL of n-heptane, at a temperature 80°C under a hydrogen-ethylene pressure of 19 bars and with MAO as activating agent. The amount of activating agent MAO was adjusted to yield a ratio [Al]:[Ti] of 2000.

Activities are expressed in kg polyethylene per mol of Ti per hour. PDI is the polydispersity index defined as the ratio Mw/Mn of the weight average molecular weight Mw over the number average molecular weight Mn.

The procedure was the same as that described above with MAO in paragraph IV.a except that an appropriate amount of diethyl zinc (ZnEt₂) was injected in the reactor before adding the catalyst. The polymerisation results are displayed in Table VIII. Run Complex [ZnEt₂]:[Ti] m Polymer (mg) Activity (kg/mol/h) DSC GPC Tm (°C) ΔH(J.g^-1) Mw Mn PDI 37 A1 100 691 1349 135 177.2 410450 29220 14.0 38 A1 250 342 668 134 190.8 155800 15460 10.1 39 A1 500 317 619 132 216.3 86450 7190 12.0 40 A1 1000 226 441 129 224.6 19410 3840 5.1

The reaction was performed with 0.5 µmol of catalyst dissolved in 5 mL of n-heptane, at a temperature 80°C under an ethylene pressure of 19 bars and with MAO as activating agent. The amount of activating agent MAO was adjusted to yield a ratio [Al]:[Ti] of 2000.
Activities are expressed in kg polyethylene per mol of Ti per hour.
PDI is the polydispersity index defined as the ratio Mw/Mn of the weight average molecular weight Mw over the number average molecular weight Mn.

Ethylene polymerisation reactions were performed in a 24 parallel reactors unit containing glass inserts of 50 ml and magnetic stirrers. In a typical reaction run, the catalyst was introduced into the glass insert. Then the activator (MAO or IBAO) and the solvent (22 to 24 ml of heptane) were added. The glass insert was sealed with a septum and placed into the 24 parallel reactors unit. While closing the reactor, the septum was pierced by a needle. The stirring was set at 1000 rpm and the temperature was set at 80°C. Then the pressure was raised to 22 bar of ethylene. These conditions were maintained during 20 min. The polymerisation results are displayed in Tables IX and X. Complex Activator PE Activity HT-GPC DSC mg ml g Kg/mmol.h Mw (Da) Mn (Da) PDI Tm (°C) B27 0.978 MAO 1.2 0.92 1.17 / B27 0.98 MAO 1.2 0.87 1.10 / C27 0.933 MAO 1.2 0.51 0.55 / C27 1.367 MAO 1.2 0.59 0.44 / A1 0.57 MAO 0.6 0.95 1.77 / A1 0.57 MAO 0.6 1.05 1.96 / A27 0.53 MAO 0.6 0.68 1.42 / A27 0.53 MAO 0.6 0.68 1.42 / D27 1.248 IBAO 2.6 0.253 0.21 / D27 1.044 IBAO 2.6 0.214 0.21 / C27 0.96 IBAO 2.6 0.104 0.11 / C27 0.953 IBAO 2.6 0.129 0.14 / A3 0.54 MAO 0.163 1.18 1.60 insoluble 135.4 A3 0.54 MAO 0.163 1.17 1.58 / A15 0.522 MAO 0.163 0.73 1.46 insoluble 137.1 A15 0.522 MAO 0.163 0.68 1.36 / D6 1.66 IBAO 2.6 1.05 0.76 / D1 1.44 IBAO 2.6 0.70 0.47 275543 11545 23.9 130.9 D1 1.55 IBAO 2.6 0.57 0.36 187629 8662 21.7 131.7 D7 1.57 IBAO 2.6 0.66 0.45 / D7 1.46 IBAO 2.6 0.66 0.49 / Conditions : Heptane 22-24 ml, 80°C, ethylene 22 bar, 20-30 min., 1000 rpm.
For GPC curves,see figure 4. Complex Activator PE Activity Kg/mmol. HT-GPC DSC Tm(°C ) mg ml g h D1 1.47 IBAO 2.6 0.19 0.13 / / D1 1.23 IBAO 2.5 0.18 0.14 Insoluble 134.1 D6 1.85 IBAO 2.6 0.11 0.07 / / Conditions : Heptane 22 ml, 50°C, ethylene 15 bar, 20-30 min., 1000 rpm.

The procedure was the same as that described above with MAO in paragraph IV.a except that the reaction was performed at 80°C, and that the reactor was first pressurised with propylene, followed by ethylene to a final pressure of 19 bar in order to obtain a mixture of 10% of propylene (molar fraction) in ethylene. The polymerisation results are displayed in Table XI. Run Complex m Polymer (mg) Activity (kg/mol/h) DSC % Me branching (°C) ΔH 41 A1 293 572 126 127.4 2.2

The reaction was performed with 0.5 µmol of catalyst dissolved in 5 mL of n-heptane, at a temperature 80°C under an ethylene pressure of 19 bars and with MAO as activating agent. The amount of activating agent MAO was adjusted to yield a ratio [Al]:[Ti] of 2000.
Activities are expressed in kg copolymer per mol of Ti per hour.

The obtained polymers were insoluble in hot trichlorobenzene and could not be caracterised by GPC.

The procedure was the same as that described above with MAO in paragraph IV.a except that an appropriate amount of vinyltrimethylsilane was injected in the reactor before adding the catalyst. The reaction was performed at 80°C and to pressure of 19 bar. The polymerisation results are displayed in Table XII. Run Complex [Silane]:[Ti] m Polymer (mg) Activity (kg/mol/h) 42 A1 500:1. 610 1191 43 A1 2000:1 740 1147

The reaction was performed with 0.5 µmol of catalyst dissolved in 5 mL of n-heptane, at a temperature 80°C under an ethylene pressure of 19 bars and with MAO as activating agent. The amount of activating agent MAO was adjusted to yield a ratio [Al]:[Ti] of 2000.
Activities are expressed in kg copolymer per mol of Ti per hour.
Typical SiMe₃ bands were observed on the infrared spectra at 835; 855 and 1248 cm^-1.